@Sunny27: Between the Lions is a great kids' show. I love it and I'm an adult! PBS also shows Mister Rogers re-runs and I highly recommend them. There's nothing like a child hearing Fred Rogers tell them in his gentle voice, "I like you, yes I do! I like you just because you're you!" Makes my day, even now.
I also love "Zaboomafoo" and "Kratts' Creatures." The Kratt Brothers do a great job of teaching nature and caring for animals on their shows. (And Mom gets to look at the brothers. They're awfully cute!)
"Angelina Ballerina" is an adorable little cartoon about a mouse ballerina and "Arthur" puts me on the floor when he has a problem with D.W., his little sister. Also, the "Thomas the Tank Engine" shows are great. These shows focus on interpersonal relations.
"The Magic School Bus" and "Reading Rainbow" are still good, and if you can find the DVDs, "Wishbone" is marvelous for introducing kids to great literature.
And, you might as well pick up the "Schoolhouse Rock" DVD. I'll bet there's hardly an adult my age who didn't learn The Preamble from singing it on "Schoolhouse Rock" on Saturday mornings. These are such great songs. They teach grammar, math, science, history and civics. I recommend them, also.